Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
  • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
  • B05D7/144—After-treatment of auto-deposited coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
  • B05D7/142—Auto-deposited coatings, i.e. autophoretic coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
  • C08F214/02—Monomers containing chlorine
  • C08F214/04—Monomers containing two carbon atoms
  • C08F214/08—Vinylidene chloride
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
  • C09D5/088—Autophoretic paints

Definitions

• This invention relates to the formation of resi­nous coatings on metallic surfaces. More specifically, this invention relates to the deposition of improved resinous coatings without need for reaction rinses on metallic surfaces by contacting the metallic surfaces with an acidic aqueous coating solution containing dispersed solid resin particles. In addition, this invention relates to improved means for curing such coatings.
• Autodeposition is a relatively recent develop­ment in the coating field whereby an aqueous resinous coat­ing composition of low solids concentration (usually less than about 10%) forms a coating of high solids concentration (usually greater than about 10%) on a metallic surface immersed therein, with the coating increasing in thickness or weight the longer the time the metallic surface is immersed in the composition.
• Autodeposition is similar to electrodeposition, but does not require the aid of exter­nal electrical current to cause the resin particles to deposit on the metal surface.
• autodepositing compositions are aqueous acid solutions having solid resin particles dispersed therein.
• Acidic aqueous coating solutions having dis­persed therein solid resin particles and having the capability of forming on metallic surfaces immersed therein resinous coatings which grow with time are disclosed in various patents.
• 4,347,172 and 4,411,937 disclose an improved autodepo­siting composition
• hydrofluoric acid comprising hydrofluoric acid, ferric iron, for example, ferric fluoride, and dispersed resin solids.
• an oxidizing agent such as peroxide is disclosed as an optional ingredient.
• U.S. Patent No. 4,180,603 discloses a coating composition containing epoxy resin solids and a cross-­linking resin which when used without a chrome after-treat­ment produces coatings capable of withstanding up to 336 hours of exposure in standard salt spray tests.
• the present invention is directed to an improvement in autodeposited coatings which are formed from resin-contain­ing coating compositions capable of forming continuous films having low moisture and oxygen permeability and which have greater corrosion resistance than has been previously obtainable without the use of a chrome after-treatment.
• U.S. Patent No. 4,191,676 discloses the effective use of baking the coating for a period of time until the metallic surface has reached the temperature of the en­vironment in which it is being heated.
• the present in­vention is related also to the improved curing of auto­deposited coatings in a manner such that savings in time and energy can be realized.
• a still further object of this invention is to provide an autodepositing composition capable of forming an autodeposited coating which does not require the use of chrome after-treatment, particularly, treatment with hexavalent chromium or mixtures of hexavalent and trivalent chromium in aqueous rinse solutions, to achieve a higher order of corrosion resistance than has been possible with the use of prior art autodepositing compositions.
• the achievement of such a goal would completely eliminate any possible health hazards which might result from the use of such chromium-­containing solutions.
• a still further object of this invention is to provide autodeposited coatings with hardness of a higher order than present in autodeposited coatings heretofore known.
• Another object of this invention is to provide autodeposited coatings with superior resistance to sol­vents, particularly those solvents which frequently cause damage to organic coatings used in the automotive industry.
• Yet another object of the invention is to provide autodeposited coatings which can be cured by immersing in hot water (for example, water at a temperature up to 100°C) or by spraying with hot water or by steam treating.
• hot water for example, water at a temperature up to 100°C
• spraying with hot water or by steam treating for example, water at a temperature up to 100°C
• Still another object of this invention is to provide a tightly adherent autodeposited coating which will withstand unusually long salt spray and water soak testing.
• the present invention comprises the use in an autodepositing composition of dispersed resin solids pre­pared from vinylidene chloride.
• One aspect of the present invention includes an autodepositing composition containing an internally stabilized vinylidene chloride copolymer.
• internally stabilized means that the vinylidene chloride­containing polymer includes an ionizable group which is part of the chemical structure of the polymer, that is, a chemically bonded part of the polymer structure. Latexes of such internally stabilized vinylidene chloride-contain­ing polymers can be prepared utilizing little or no surfactant.
• An example of such a latex is characterized by having therein particles of resin which are prepared by copolymerizing (A) vinylidene chloride with (B) monomers selected from the group consisting of methacrylic acid, methyl methacrylate, acrylonitrile, and vinyl chloride and (C) a water soluble ionic material which includes an inorganic ionizable group, for example, such as is present in sodium sulfoethyl methacrylate, and which is copolymer­izable with (A) and (B).
• Another aspect of the present invention includes an autodepositing composition containing a vinylidene chloride copolymer stabilized with an external surfactant, such copolymer containing at least about 50 wt.% vinyli­dene chloride.
• the autodepositing composition is prepared from a latex which contains such copolymer in the form of dis­persed resin solids and in which the amount of surfactant is below the critical micelle concentration.
• Still another aspect of the present invention includes an autodepositing composition which includes, in the form of dispersed resin solids, a copolymer comprising at least about 50 wt.% of vinylidene chloride, the compo­sition containing little or no surfactant in the aqueous phase.
• the present invention includes also the use of autodepositing compositions to form on metallic surfaces autodeposited coatings having improved properties, parti­cularly improved corrosion properties.
• autodeposited coatings having improved corrosion resistance can be formed in the absence of a chrome after-treatment or other type after-treatment designed to improve the corrosion resistant properties of autodeposited coatings.
• the present invention relates also to auto­deposited coatings which are characterized by being essentially chromium-free, but having, nevertheless, a relatively high degree of corrosion resistance.
• Coating compositions within the scope of the present invention comprise the use of a particular kind of resin or latex in combination with other ingredients which are effective in providing stable autodepositing composi­tions that can produce hard, uniform, solvent resistant coatings on steel with an unusually high degree of corrosion resistance.
• coating compositions within the scope of the present invention and containing a relatively small amount of resin solids, for example, about 3-8 wt.% are effective in forming on a metallic surface immersed therein a resinous coating which grows in thickness at a relatively fast rate, producing, for example, a coating having a thickness of as much as 12.7 to 25.4 ⁇ m (0.5 to 1 mil) or more when the metallic surface is immersed in the composition for as short a time as about 90 seconds.
• the coating compositions within the scope of the present invention provide coatings with far superior corro­sion resistance than could previously be obtained by the use of autodeposition.
• the corrosion resistance of coatings formed by the present process is so dramatically improved that the process may be used in applications which previ­ously were reserved for coating only by electrodeposition.
• Coating compositions using vinylidene chloride copolymer in accordance with this invention also permit substantial savings by reducing the typical processing sequence to four stages, and lowering the curing temperature, for example, to 120°C, and lower.
• Coatings produced in accordance with the present invention from vinylidene chloride copolymers provide excellent hardness and scratch resistance as well as excel­lent appearance and solvent resistance.
• the acidic aqueous coating compositions of the aforementioned type function to attack and dissolve from a metallic surface contacted therewith metal ions in an amount sufficient to directly or indirectly cause resin particles in the region of the metallic surface to deposit theron in a continuous fashion, that is, in a manner such that there is a buildup in the amount of resin deposited on the surface the longer the time the surface is in contact with the composition.
• This deposition of the resin on the metallic surface is achieved through chemical action of the coating composition on the metallic surface.
• the use of electricity which is necessary for the operation of electrocoating methods is not required.
• the basic constituents of an autodepositing composition are water, resin solids dispersed in the aqueous medium of the composition and activator, that is, an ingredient(s) which converts the water/resin composition into one which will form on a metallic surface a resinous coating which increases in thickness or weight the longer the surface is immersed in the composition.
• activators or activating systems are known, for example, as reported in U.S. Patent Nos.: 3,592,699; 3,709,743; 4,103,049; 4,347,172; and 4,373,050.
• the activating system generally comprises an acid/oxidizing system, for example: hydrogen peroxide and HF; HNO3; and a ferric-­containing compound and HF; and other soluble metal-contain­ing compounds (for example, silver fluoride, ferrous oxide, cupric sulfate, cobaltous nitrate, silver acetate, ferrous phosphate, chromium fluoride, cadmium fluoride, stannous fluoride, lead dioxide, and silver nitrate in an amount between about 0.025 and about 50 g/l) and an acid that can be used alone or in combination with hydrofluoric acid, and including, for example, sulfuric, hydrochloric, nitric, and phosphoric acid, and an oranic acid, including, for example, acetic, chloracetic, and trichloracetic.
• an acid/oxidizing system for example: hydrogen peroxide and HF; HNO3; and a ferric-­containing compound and HF
• the preferred activating system comprises a ferric-containing compound and hydrofluoric acid.
• a preferred autodepositing composition comprises a soluble ferric-containing compound in an amount equivalent to about 0.025 to about 3.5 g/l ferric iron, most preferably about 0.3 to about 1.6 g/l of ferric iron, and hydrofluoric acid in an amount sufficient to impart to the composition a pH within the range of about 1.6 to about 5.0.
• ferric-containing compounds are ferric nitrate, ferric chloride, ferric phosphate, ferric oxide, and ferric fluoride, the last mentioned being preferred.
• U.S. Patent Nos. 4,347,172 and 4,411,937 which disclose the aforementioned type of preferred activating system disclose the optional use in the composition of an oxidizing agent in an amount to provide from about 0.01 to about 0.2 oxidizing equivalent per liter of composition.
• Suitable oxidizing agents are those commonly known as depolarizers. Examples of oxidizing agents are hydrogen peroxide, dichromate, permanganate, nitrate, persulfate, perborate, p-benzoquinone and p-nitrophenol. Hydrogen peroxide is mentioned as preferred.
• the preferred compo­sition for use in the present invention does not include the use of an optional oxidizing agent as disclosed in the aforementioned '172 and '937 patents.
• the preferred class of resins for use in the present invention is the internally stabilized class.
• internally stabilized polymers or resins include as part of their chemical structure a surfactant group which functions to maintain polymer particles or resin solids in a dispersed state in an aqueous medium, this being the function also performed by an "external surfactant", that is, by a mater­ial which has surface-active properties and which is adsorbed on the surface of resin solids, such as those in colloidal dispersion.
• An advantage of internally stabilized vinylidene chloride-containing poly­mers is that stable aqueous dispersions, including acidic aqueous dispersions of the type comprising autodepositing compositions, can be prepared without utilizing external surfactants.
• sur­factant wetting agent, emulsifier or emulsifying agent and dispersing agent.
• surfactant is intended to be synonymous with the aforementioned.
• Various types of internally stabilized vinylidene chloride-contain­ing polymers are known and species thereof are available commercially. In accordance with the present invention, they can be used to excellent advantage in realizing impor­tant improvements in the field of autodeposition.
• Surfactant groups which function to maintain polymeric particles in dispersed state in aqueous medium include organic compounds which contain ionizable groups in which the anionic group is bound to the principal organic moiety of the compound, with the cationic group being a constituent such as, for example, hydrogen, an alkali metal, and ammonium.
• exemplary anionic groups of widely used surfactants contain sulfur or phos­phorous, for example, in the form of sulfates, thiosulfates, sulfonates, sulfinates, sulfaminates, phosphates, pyrophos­phates and phosphonates.
• Such surfactants comprise inorganic ionizable groups linked to an organic moiety.
• the ionizable groups which function to internally stabilize in aqueous medium dispersed solids of the resin will involve reacting vinylidene chloride with a monomeric sur­factant and optionally one or more other monomers.
• the monomeric surfactant comprises a material which is polymerizable with monomeric vinylidene chloride or with a monomeric material which is polymerizable with monomeric vinylidene chloride and which is ionizable in the reaction mixture and in the acidic aqueous medium com­prising autodepositing compositions.
• Exemplary conditions used in fusing coatings produced ac­cording to the present invention are temperatures within the range of about 20°C to 120°C for periods of time within the range of about 10 to about 30 minutes, depending on the mass of the coated part. Baking the coating for a period of time until the metallic surface has reached the temperature of the heated environment has been used effec­tively.
• infrared radiation curing it is possible to overcome this problem by resorting to infrared radiation curing. In this case, it is possible to cure the coating without simultaneously raising the temperature of the metal to the required tem­ perature.
• infrared radiation curing is practicable only for simple geometric shapes since the area to be cured must be exposed to the infrared. In using infrared radia­tion curing, all coated surfaces must be visible to the infrared source, that is, the entire coated surface must "see" the infrared.
• Vinylidene chloride-containing resins within the scope of the present invention can have Tg's within the range of about -1.2°C (30°F) to about 29.4°C 85°F. They can also have an accelerated cure temperature of no greater than about 149°C 300°F. With respect to resins having a Tg well below room temperature, improvements can be realized by curing with water having a temperature of at least about 21.1°C (70°F). In general, however, it is believed that most curing applications will utilize hot water, for example, water having a temperature of 37.7°C (100° F) or more.
• rinsing the freshly formed autodepos­ited coating to remove therefrom residuals and curing of the coating according to the present invention can be combined into one step.
• rinsing and curing can be done simultaneously by spraying with hot water or immersing the freshly formed autodeposited coated surface in a hot water bath.
• the present invention con­templates also utilizing the curing process of the present invention in combination with heretofore known curing methods.
• a short treating time in accordance with the curing method of the present invention can be used to quickly heat the coating (which surprisingly can result in drying of the coating) followed by baking.
• the moisture vapor permeability and water sensitivity of vinylidene chloride copolymer films can be deleteriously affected by increasing concentrations of surfactant used in the process for preparation of the vinylidene chloride-con­taining polymer.
• surfactant used in the process for preparation of the vinylidene chloride-con­taining polymer.
• high surfactant concentrations are also undesirable in autodeposition.
• the latex used in formulating the composition and the autodepositing compo­sition itself contain a very low concentration of surfac­tant or no surfactant.
• the vapor permeability, as measured by cast film water vapor transmission rate (WVTR), of preferred resins is less than about 50 g/25.4 ⁇ m/m2/day and preferably less than 20 g/25.4 ⁇ m/m2/day.
• the film of these preferred resins when applied in accordance with the preferred autodepositing method of this invention, that is, the method which utilizes an autodepositing composition containing an hydrofluoric acid/ferric fluoride activating system, provides a coated surface in which the vapor permeability, based upon im­proved corrosion resistance is substantially less than that of a film cast from the same latex.
• Such autodeposited coatings differ from coatings formed from autodepositing compositions containing externally stabilized resins.
• autodeposited coatings formed from externally stabilized resins comprise resin molecules which are joined by metal atoms which link together negatively charged hydrophilic groups of the surfactant molecules which are adsorbed on the surfaces of different resin molecules.
• the source of the metal atom is the metal substrate being coated as metal is dissolved therefrom during formation of the coating.
• the joining of such resin molecules is based on physical bonding in that the surfactant is physically adhered to the surface of the resin particle.
• the latex used contains a vinylidene chloride copolymer which is prepared by copolymerization with a water soluble ionic stabilizer such as sodium sulfoethyl methacrylate.
• a com­position was prepared by admixing the following:
• the Aquablak S dispersion (available from Borden) was thinned with an equal weight of deionized water to pro­duce a consistency approximately equal to that of the latex. While stirring continuously, the latex was slowly added to the diluted black pigment dispersion. The total elapsed time of mixing to prepare a 1 liter bath is approximately one minute. The mixing time is not critical to the prepar­ation of performance of the bath, but is mentioned here merely to point out that careful and reproducible procedures should always be used in the preparation of a coating compo­sition to assure uniformity from batch to batch. When the black pigment dispersion has been uniformly blended with the polymer latex, deionized water is added with continuous stirring.
• Mild steel test panels for example, unpolished cold rolled Q-panels which are commercially available, are cut to 7.5 cm by 10.2 cm (3-inch by 4-inch) size and cleaned in heated alkaline cleaner solution by immersion or spray application or both. The panels are then rinsed with water. The panels are then immersed in the coating composition of Example 1 for 90 seconds. When the panels are removed from the coating composition, they are rinsed with water and baked for 10 minutes at 100°C.
• This example illustrates the excellent solvent resistance of the autodeposited coatings of Example 2.
• coatings of the present invention are compared with commercially available autodeposited coatings by subjecting them to the action of various solvents fre­quently encountered by automobiles.
• the conditions used for each solvent represent the more difficult tests to which automotive manufacturers subject coatings.
• the pencil hardness of the coating is measured before and after ex­posure to the solvents with the following results.
• This example shows the relationship between the coating thickness produced by immersion of mild steel panels into the composition of Example 1 and the time of immersion.
• the scribe ratings indicate the loss of coating at the scribe in millimeters when the panels are removed from the salt spray cabinet and immediately scraped vigorously by holding a spatula with its blade at 90° to the coated surface and scraping the coating back and forth until all loosely adhering material is removed.
• the above ratings are all excellent.
• the field ratings are based on the number and size of rust spots over the entire panel with 0 representing total failure and 10 representing no failure whatever. The above ratings are very good.
• Example 2 mild steel panels were immersed in a composition as described in Example 1 to produce coatings having a uniform thickness of 10.2 ⁇ m (0.4 mil). The panels were then subjected to salt spray testing (ASTM B-117) for various lengths of time. The panels were then rated for loss of adhesion at the scribe and amounts of corro­sion on the remainder of the panel. The results are as follows.
• Coatings were autodeposited from a composition like Example 1 to produce coatings of the following thick­nesses: 8.9; 12.7; 17.8; and 25.4 ⁇ m (0.35; 0.5; 0.7; and 1.0 mil).
• the freshly autodeposited uncured coatings were then subjected to the above rinsability test. There wasn't any sign of failure either by redispersion or loss of coating integrity at any of the coating thicknesses tested. This test cannot be consistently passed by prior art freshly formed autode­posited coatings.
• This example describes the rapid, energy efficient method of curing autodeposited coatings of the present invention by hot water.
• Coatings of 12.7 ⁇ m (0.5 mil) thickness were formed by immersion of thick-walled hot rolled steel parts into a composition like that of Example 1.
• the procedure used was as follows: cleaned in hot alkaline cleaner; rinsed in tapwater; autodeposited for 90 seconds; rinsed in tap­water; and immersed for 5 seconds in water at 85°C (185°F).
• Coat­ing properties such as, for example, salt spray resistance, were equivalent to those obtained by baking.
• salt spray testing ASTM B-117
• the parts showed less than 1 mm of adhesion loss at the scribe or a rating of 9-plus out of 10, and the remainder of the part was excel­lent with no signs of corrosion.
• coatings of 12.7 ⁇ m (0.5 mil) thickness were autodeposited on cold rolled mild steel panels by immersion in a composition like that of Example 1 for 90 seconds. After removal from the coating bath, the panels were allowed to stand in air for 60 seconds to permit the supernatant coating composition to react completely with the metal surface. The panels were then rinsed in tap­water and placed in a low pressure steam chamber for curing. In two cases, oven curing was used with or without steam curing. The panels were then scribed and placed in salt spray for 168 hours and 336 hours. The following table lists the results.
• the following acidic aqueous coating composition was prepared by combining
• the resin of the latex used in the above composition comprises a copolymer of vinylidene chloride, vinyl chloride, ethylhexyl acrylate or methacrylate, and acrylic acid.
• the vinylidene chloride content may vary from 60 to 76 weight %.
• the ethylhexyl acrylate or metha­crylate may vary from 4-10 weight %.
• the acrylic acid may vary from 1 to 4 weight %.
• the latex is externally stabil­ized by the adsorption of sodium lauryl sulfate on the resin particles.
• the black pigment dispersion comprises a fine particle furnace black dispersed in water by an anionic surfactant.
• This example shows the physical properties of coatings formed by autodeposition from the composition of Example 12. Coatings were autodeposited to a film thick­ness of 22.9 ⁇ m (0.9 mil) in 90 seconds. After curing at 90°C for 10 minutes, the coatings showed near specular gloss with readings of 90 to 95% reflectivity at 60° using a Gardner Colorguard meter. The coatings were impacted with a Gardner Coverall impact tester using a (12.7 mm) (half-inch) diameter ball at 18 N ⁇ m (160 inch-pounds).
• This example illustrates the formulation and deposition of high gloss, colored coatings based on the type of latex of Example 12.
• the following procedure is used to prepare the above compo­sition. Adjust the pH of the latex to 7.1 by addition of 2% ammonia solution. In a separate container, dilute the pigment with just enough deionized water to induce the paste to flow. Stir in the Dowfax 2Al surfactant (sodium salt of an alkylated diphenyl oxide disulfonate). While agitating the latex, slowly stir in the pigment dispersion. When the color is uniform, add the water. Finally, stir in an aqueous solution containing the ferric fluoride and the hydrofluoric acid.
• This example illustrates the high corrosion resistance of autodeposited coatings formed from a compo­sition like that of Example 11.
• Clean, mild steel panels were immersed in the coating composition for 90 seconds. They were then baked at 90°C for 15 minutes. Salt spray performance after various exposure times is shown in the following table. This performance is superior to that of autodeposited coatings formed from prior art compositions. Treatment with chromium solutions were not required to obtain this perfor­mance and the curing temperature used was 70 Centigrade degrees cooler than is used by current commercial autodep­ositing finishing lines.
• the latex has a high vinylidene chloride content which is reflected in the density of the latex which is 1.250 kg/dm3 (10.43 lbs per gal).
• the low concentration of surfactant in the aqueous phase or serum is shown by the high surface tension, 52 mN/m (dynes/cm).
• Cold rolled, mild steel panels were treated as follows: cleaned in hot alkaline solution; rinsed with water; immersed in the above autodepositing composition for 90 seconds; allowed to stand in air for two minutes; rinsed with water; and baked for 10 minutes at 120°C.
• the cured coatings which were 30.5 ⁇ m (1.25 mils) thick, were subjected to salt spray testing for various periods of time, as reported in the following table. This is excellent performance despite the fact that no chromium-containing solutions were used to improve the corrosion resistance and the curing temperature was 40 to 80° Centigrade degrees lower than that used in curing prior art autodeposited coatings.
• the next group of examples illustrates the pre­paration of various latexes which include particles of resin comprising copolymers prepared from vinylidene chlor­ide and other monomers by emulsion polymerization reactions which include relatively small amounts of emulsifier.
• This group of examples illustrates also the preparation of autodepositing compositions containing the latexes and the evaluation of autodeposited coatings formed there­from.
• each of the following initiator solutions was added to the reaction vessel: (A) 0.3 kg of a solution consisting of 0.025 kg sodium disulfite in 2 kg of demineralized water; and (B) 0.62 kg of a solution of 0.05 kg ammonium peroxydisulfate in 4 kg of demineralized water.
• the temperature of the reaction mixture increased to about 35°C.
• the remaining 32 kg of the monomeric mixture and the remainder of each of the aforementioned solutions were added to the reaction vessel.
• the monomeric mixture was added over about a 2-hour period, whereas the addition of each of the initiator solutions was completed after about 50 minutes.
• reaction temperature did not increase above about 37°C.
• reaction temper­ature was raised to 50°C and maintained for about 30 minutes.
• product of reaction was distilled briefly at about 15°C under reduced pressure. The 40% emulsion thus obtained con­tained less than 1 wt.% coagulate.
• Autodepositing compositions were prepared from each of the latexes of Table 1 as follows. Two hundred grams of latex were diluted with 400 ml of distilled water. Fifty ml of activator solution composed of water, 15 ml of a 21 per­cent solution of hydrofluoric acid and 4.1 grams of ferric fluoride were diluted with about 100 ml of water and then slowly poured into the latex mixture. Distilled water was then added to make the final volume of the coating bath 1 liter. Steel panels were autophoretically coated therein, and the coatings were cured for 5 min at 100°C without previous rinsing in a chromate solution. The coated panels were sub­jected to a salt spray test according to ASTM 117-73 for 120 hours.
• An autodepositing composition comprising an acidic aqueous solution having dispersed therein resin solids of an internally stabilized vinylidene chloride copolymer.
• a composition wherein said copolymer comprises vinylidene chloride and one or more monomers selected from the group consisting of vinyl chloride, acrylic acid, methacrylic acid, methylacrylate, ethylacrylate, butylacrylate, methyl methacrylate, acryla­mide, methacrylamide, acrylonitrile and methacrylonitrile.
• composition wherein said water-­soluble copolymerizable material is sulfoethylmethacrylate.
• a composition wherein said vinyli­dene chloride comprises at least about 45% by weight of said copolymer based upon the total weight of said copolymer.
• a composition comprising an aqueous solution of hydrofluoric acid, ferric iron and about 3 to about 10% by weight of said internally stabilized vinylidene chloride copolymer.
• a composition wherein said copolymer is crystalline.
• a composition which includes hydrofluoric acid and ferric fluoride which includes hydrofluoric acid and ferric fluoride.
• An autodepositing composition comprising an aqueous solution of hydrofluoric acid and ferric fluoride having dispersed therein resin solids of an externally stabilized copolymer of vinylidene chloride, the vinylidene chloride content thereof being in excess of 50 wt.% of said copolymer.
• a composition wherein said copoly­mer includes one or more co-monomers selected from the group consisting of vinyl chloride, acrylic acid, methylacrylate, ethylacrylate, butylacrylate, methacrylic acid, methyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and methacrylamide.
• a composition wherein the vinyli­dene chloride content of said copolymer is no greater than about 95 wt.% of said copolymer.
• a composition wherein said surfac­tant is sodium lauryl sulfate.
• a composition wherein said copolymer is crystalline.
• a composition including also pigment particles dispersed therein.
• a process for autodepositing resin particles onto a metallic surface comprising immersing said metallic surface into an autodepositing composition and allowing said metallic surface to remain in said composi­tion until the coating of autodeposited resin particles has built to the desired thickness.
• said resin includes a copolymer of vinylidene chloride, a monomeric sulfonate surfactant and one or more of vinyl chloride, acrylic acid, methacrylic acid, methylacrylate, methyl methacrylate, ethylacrylate, butylacrylate, acrylo­nitrile, methacrylonitrile, acrylamide and methacrylamide dispersed in an aqueous solution of hydrofluoric acid and ferric fluoride.
• a process wherein said metallic surface is a ferriferous surface.
• a process wherein said metallic surface is a ferriferous surface.
• An autodeposited coating comprising a cured, internally stabilized vinylidene chloride-containing resin adhered to a metallic surface, said resin comprising a plurality of polymeric molecules having a plurality of negatively charged groups in chemically bonded form, including polymeric mole­cules of resin contiguous to said surface chemically bonded thereto by a plurality of said negatively charged groups, and polymeric molecules of resin comprising said coating chemically bonded together through said negatively charged groups, said groups being chemically linked by metal atoms, the source of which is said metallic surface, said coated surface being substantially free of chromium and having cor­rosion resistance properties characterized by less than about 1mm loss of adhesion at the scribe when subjected to 5% neu­tral salt spray at 95°F ASTM B-117 for 500 hours or more.
• An autodeposited coating comprising a cured, inter­nally stabilized vinylidene chloride-containing crystalline resin adhered to a metallic surface.
• a cured autodeposited coating adhered to a metallic surface and formed according to the above process.
• a coating wherein said metallic surface is a ferriferous surface.
• a coating wherein said metallic surface is a ferriferous surface.
• a coating wherein said metallic surface is a ferriferous surface.
• a process for curing an autodeposited coating comprithsing subjecting an uncured autodeposited coating to steam or water having a temperature of about 21°C (70°F) to about 100°C (212°F).
• a process wherein said coating is cured by immersion in water at a temperature of about 21°C (70°F) to about 100°C (212°F).

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• 1984
  • 1984-07-24 EP EP87119197A patent/EP0310708A3/de not_active Ceased

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